US4690888A - Silver halide color photo-sensitive material - Google Patents

Silver halide color photo-sensitive material Download PDF

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Publication number
US4690888A
US4690888A US06/774,340 US77434085A US4690888A US 4690888 A US4690888 A US 4690888A US 77434085 A US77434085 A US 77434085A US 4690888 A US4690888 A US 4690888A
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Prior art keywords
silver halide
photographic material
layer
dye
photo
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Mitsuto Fujiwhara
Takao Nimura
Yasumasa Numata
Yasuko Matsubara
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/27—Gelatine content

Definitions

  • This invention relates to a silver halide color photosensitive material (hereinafter referred to as photographic material), and more particularly to a photographic material which can automatically form a color image and an unsharp mask.
  • French Pat. No. 2,260,124 has disclosed a photographic material which was made by orderly laminating a physical developing nuclei-containing layer which contains a ballasted coupler, a layer which contains a scavenger for the oxidized of color-developing agents, and a photo-sensitive silver halide emulsion layer which contains a ballasted coupler.
  • a color negative image is obtained by exposing and color-developing using a first color developer which does not contain any silver halide solvent, and then the unsharp positive image is obtained by physical color-development using a second color developer which contains a silver halide solvent, as a method desirable to obtain a color negative image and an unsharp positive image using said photographic material.
  • the absence of such a scavenger would cause part of the oxidized color-developing agents, which are produced in the exposure areas, to disperse into the physically color-developing nuclei-containing layers, and, consequently, would cause an unsharp negative image to form therein by color-developing reaction, resulting in failure to obtain both color negative and unsharp positive images as desired.
  • the absence of the scavenger would make it difficult to improve the image sharpness because of its difficulty to make the material thinner due to the essentiality of the three layers including said scavenger-containing layer.
  • This invention aims at resolving drawbacks of the prior art as described above.
  • Another object of the invention is to provide a photographic material which gives very sharp images with a fewer number of essential layers.
  • a further object of the invention is to provide a photographic material which can form both color negative and unsharp positive images of good quality through the only one developing process.
  • the photographic material of the invention is a silver halide color photo-sensitive material having both of ballasted couplers combined with photo-sensitive silver halide emulsions, and colored compounds to be reacted with oxidized developing agents, and is characterized in that said colored compounds are compounds capable of slightly diffusing in said photographic material during developing treatments.
  • to diffuse during developing treatments means that, during the picture-making processes, preferably a developing process, said colored compound diffuses by 1 ⁇ m or more, preferably by 5 ⁇ m or more, but at least 30 wt% of its used amount remains in the photographic material still after developing treatments.
  • the compound which is a colored compound that reacts with the oxidized developing agent, and is capable of slightly diffusing in the photographic material during developing treatments is described.
  • the compound of the invention it is referred to as the compound of the invention.
  • the compound of the invention is a colored compound which has its primary absorption in the primary absorption region of the dye that is produced by the reaction between the above-mentioned ballasted coupler and the oxidized color developing agent.
  • the compound of the invention forms a colored or colorless product by the reaction with the oxidized developing agents. And when the reaction product has a color tone undesirable in view of the image formation, the reaction product diffuses out of the photographic material. Hence in areas where color images are produced by the reaction between the oxidized color developing agent and the ballasted coupler, the compound of the invention also reacts with the oxidized developing agent to form the reaction product which either is noncolored, or colored but diffusible out of the photographic material.
  • the compound of the invention In areas where color images are not produced from the ballasted coupler, the compound of the invention remains not to react but diffuses slightly. Consequently, the compound of the invention forms color images opposite to those from said ballasted coupler; the former are positive images when the latter are negative images, for example. In addition the compound of the invention forms unsharp images, namely unsharp mask images because of its dispersibility.
  • A is an organic residue which releases the component of Link-B on reacting with the oxidized developing agent corresponding to the amount of the oxidized developing agent.
  • B is another organic residue, and Link is a group which links A and B groups together.
  • a compound expressed by General Formula [1] is a colored compound which is capable of slightly diffusing in the photographic material during developing treatments.
  • the compound is equipped with substituent group(s) which balance between hydrophilic and lipophilic properties so that its reaction product may diffuse out of the material system after the reaction, provided that any product from A or Link-B group could constitute any compound which presents undersirable color tone in view of the image formation.
  • residues of compounds including, for example, phenols, naphthols, 5-pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, indazolones, acylacetanilides; compounds expressed by RCOCH 3 , where R is, for example, an alkyl, aryl or heterocyclic group; and compounds expressed by: ##STR1## Where Z is, for example, a group of atoms which constitute a 5- to 8-member saturated or unsaturated, alicyclic or heterocyclic group, and R' is an aryl residue.
  • Link groups there are cited, for example, --N ⁇ N--, --O--, --S--, --NH--SO 2 --, --SO 2 --NH--, --CH ⁇ , ##STR2## and groups expressed by: ##STR3## Where ##STR4## is a nitrogen-containing heterocyclic residue such as succinic imidoyl, phthalic imidoyl, pyridoyl, imidazolyl, imidazolonyl, benzimidazolyl, hydantoyl, thio-hydantoyl, triazolyl, benzotriazolyl, urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl, or tetrazolyl; R is a group such as alkyl or aryl group which may be allowed to have substituent group(s).
  • the B group is an organic residue, for example, an aryl or heterocyclic group, which may be allowed to have auxochrome(s), or a dye residue, when the Link group is a chromophore such as --N ⁇ N-- or --CH ⁇ . It is preferably a residue of dye such as azo, anthraquinone, azomethine, indophenol or indoaniline dye, when the Link is not a chromophore.
  • a compound which is expressed by General Formula [I], and has such a constitution as above can be a colored substance owing to its B group or A-Link-B as a whole.
  • a compound expressed by General Formula [I] may be provide with a property to slightly diffuse during developing treatments, and with a diffusibility to cause undesirable reaction products in case of the products is produced, to diffuse out of the material, such an alkali-soluble group as carboxyl, sulfo, hydroxyl or sulfamoyl group, and such a diffusibility-reducing group as alkyl group may be properly introduced to balance its diffusibilities before and after the reaction.
  • the compounds of the invention are classified into the following types, for example, according to their properties.
  • Such a compound has preferably both alkali-soluble group(s) and an organic residue, such as alkyl group(s) with, for example, 16 or less carbon atom so as to exhibit slight diffusibility in the photographic material.
  • an organic residue such as alkyl group(s) with, for example, 16 or less carbon atom so as to exhibit slight diffusibility in the photographic material.
  • alkali-soluble group(s) are contained by the A group, or that a color developing agent having alkali-soluble group(s) is employed, so that said dye may diffuse out of the material during developing treatments.
  • alkali-soluble group(s) are contained by the B group, so that the B groups after reaction may diffuse out of the material.
  • Type A Colored Coupler
  • the Coup group of General Formula [II] is a coupler residue, preferably having alkali-soluble group(s), and the dye produced there from by color development diffuses out of the photographic material.
  • the Ar group is preferably an aryl group such as benzenoid or naphthlenoid group, allowably having substituent group(s), or a heterocyclic group such as isooxazole group, allowably having substituent group(s), and in addition, preferably has semi-ballasted group(s), so that said compound of General Formula (II) may slightly move in the photographic material.
  • the Link 2 Group is --N ⁇ N-- or --CH ⁇ .
  • the hue, which is exhibited by the dye produced from the coupler on reaction with the oxidized color developing agents, is the primary absorption for image formation, the dye there-from does not move in principle, and the hue exhibited by the colored coupler itself is due to a secondary absorption different from said primary absorption region.
  • the dye produced from the Coup group essentially diffuses out of the material, and so the hue exhibited by the compound of General Formula [II] is necessarily identical with the primary absorption of the color image.
  • the photo-sensitive region of the silver halide layer combined with the compound of the invention is complementary to the hue from the compound of the invention in a case of a conventional negative photographic material, for example.
  • a yellow compound is employed as a colored coupler in said prior art, while a magenta compound is employed in the invention. This difference will be easier understood by further description according to Example later.
  • Type B Active Site Substitution Type
  • the Coup group of General Formula [III] is the same as that of General Formula [II].
  • the Link 3 also is synonymous with the Link of General Formula [I], and preferably a group such as --O--, --SO 2 --NH--, or --NHSO 2 -- which becomes alkali-soluble after coupling reaction.
  • the Dye is a dye part, and preferably has alkali-soluble group(s), which are not always essential according to the type of the Link 3 .
  • the compound of General Formula [III] preferably has semi-ballasted group(s) so that it may slightly diffuse in the photographic material.
  • Said semi-ballasted group(s) are preferably attached to the group more diffusible between the dye produced on color development and the Link 3 -Dye group.
  • Type C White Coupler Type
  • the W coup of General Formula [IV] is, for example, a residue expressed by R 2 COCH 2 --, where R 2 is a group such as alkyl, aryl or heterocyclic group with 16 or less carbon atoms; or by the following formula: ##STR5## where Z is a group of atoms which constitute a 5- to 8-member alicyclic, condensed-ring or heterocyclic residue, and R 3 is an aryl residue,
  • the Link 4 is --O--, --S--, or --SO 2 --.
  • the Dye is a dye residue, preferably having alkali-soluble group(s).
  • the Link 4 -Dye diffuses out of the photographic material.
  • such a compound preferably has semi-ballasted group(s) which cooperate with alkali-soluble group(s) that may be attached to the Dye part, so that said compound itself may slightly move in the layer; it is especially preferable that said compound has said semi-ballasted group(s) in its W coup part.
  • a compound which belongs to this class is not submitted to any coupling reaction dissimilarly to the compound of CLASS I or II. Instead, it reacts with the oxidized developing agent to produce the oxidation product such as a quinone or quinoneimide compound which, in turn, releases the dye only by an reaction with alkali in the developer, or an intramolecular ring-closing reaction.
  • the oxidized developing agent such as a quinone or quinoneimide compound which, in turn, releases the dye only by an reaction with alkali in the developer, or an intramolecular ring-closing reaction.
  • Type D DRR Compound Type
  • the FUN group of General Formula [V] is preferably a redox compound moiety such as 2-, 3-, or 4-phenol; 4- ⁇ -naphthol, 1- ⁇ -naphthol, 2-hydroquinone, 3-indole, or 4-pyrazolone-5 residue; the Link 5 group is --NHSO 2 -- (where the nitrogen atom is combined with the Fun part), --O--, --SO 2 --, or --S---; the Dye group is preferably a dye residue, and has alkali-soluble group(s).
  • Exemplary Compound (11) is cited as an exemplification of III-D, but it is also an exemplification of I-B because it can also couple with the oxidant of a color developing agent.
  • Compound 2 which was of yellow powder and had 425 nm at ⁇ max in ethyl acetate, was prepared in such a manner that p-t-butoxyaniline in place of anthranilic acid hexyl ester was diazotized and whereto 1-phenyl-3-phthaloylamido-5-pyrazolone was coupled; and Compound 4, which was of red powder and had 525 nm at ⁇ max in methanol, was prepared in such a manner that a diazonium salt of 1-hydroxy-4-(4-aminophenoxy)-2-(2-dimethylamino-4-sulfo)-1-naphthanilide is coupled to N-decanoylamino H acid.
  • a photographic material of the invdention has been a ballasted coupler combined with a photo-sensitive silver halide emulsion, and a compound of the invention.
  • the ballasted coupler is preferably contained by the photo-sensitive silver halide emulsion layer.
  • the compound of the invention is contained by said silver halide emulsion layer and/or another photograph-constituting layer than said silver halide emulsion layer.
  • Said different photograph-constituting layer is not essentially but preferably a layer adjacent to said silver halide emulsion layer, and preferably situated on the side opposite to the incidence of exposure.
  • Said different photograph-constituting layer is allowed to be either another photo-sensitive silver halide emulsion layer being similar to said photo-sensitive halide emulsion layer in its photosensitivity, or a photo-insensitive layer.
  • the compound of the invention When the compound of the invention is contained by such a photo-insensitive layer, it reacts with developing agent(s) among various used developing agents, which diffuse into said photo-insensitive layer to form an unsharp mask image.
  • the using amount of the compound of the invention is preferably 0.01 to 1.00 mole, especially 0.05 to 0.60 moles per mole of the ballasted coupler to be combined with said compound. It can be added in a way similar to the case of the ballasted coupler as mentioned later.
  • the silver halide for photo-sensitive silver halide emulsions used in the invention is allowed to be any compound among silver bromide, silver iodobromide, silver iodochlordbromide, silver chlorobromide and silver chloride.
  • the particles of the silver halide are allowed to have either a regular crystal form such as cubic, octahedral or tetra decahedral system; or an irregular crystal form such as sphere or plate.
  • the particles of the silver halide are allowed either to be composed of a complex of the above forms, or to be a mixture of various crystals. In addition, they are allowed to be composed of either a throughly homogeneous structure, or a laminarly heterogeneous structure from inside through outside.
  • silver halide particles are useful regardless of having properties to make latent images form mainly on inside or on outside.
  • the silver halide emulsion of the invention is useful regardless of its particle size distribution.
  • Either emulsion with a wide particle size distribution (called polydisperse emulsion) or emulsion with a narrow particle size distribution (called monodisperse emulsion) is evenly useful.
  • the monodisperse emulsion is referred to that it has a 0.15 or smaller value as the quotient of the standard deviation of the particle size distribution by the mean particle size.
  • Said particle size is presented as the diameter for a spherical particle, and as the diameter of the sphere with the projected area identical with said particle for a nonspherical particle.
  • Both polydisperse and monodisperse emulsions are useful eitheir separately or in the form of mixture of two or more of them.
  • the silver halide used in the invention is allowed to be chemically sensitized. In addition, it can be also sensitized optically in a desired wave region using a dye known as a sensitizing dye in the field of the photographic art. Such sensitizing dyes are applicable either separately or in the combination of two or more of them.
  • a certain compound which is either dye having no spectral sensitizing effect in itself, or compound that does not substantially absorb any visible light, but is a supersensitizer that enforces the sensitizing effect of the sensitizing dye is allowed to be contained by the emulsion together with said sensitizing dye.
  • various hydrophilic colloidal materials as well as gelatin are useful.
  • gelatin materials include not only gelatin itself but also various gelatin derivatives such as gelatin's reaction products with various acid anhydrides, isocyanates, or active halogen atom-containing compounds.
  • acid anhydrides used in the reaction with gelatin there are cited maleic, phthalic, benzoic, acetic, isatoic and succinic anhydrides, for example.
  • isocyanates there are cited phenyl, p-bromophenyl, p-chlorophenyl, p-tolyl, p-nitro phenyl, and naphthyl isocyanates, for example.
  • active halogen atom-containing compounds such various compounds as benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesjlfonyl chloride, m-nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene- ⁇ -sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminobenzenesulfonyl chloride, 2-carboxy-4-bromo benzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-amino-5-methylbenzenesulfonyl chloride, phthaloyl chloride, p-
  • hydrophilic colloid to make the silver halide emulsion varied other substances may be used at need besides such gelatin derivative as mensioned above, and common photographic gelatins.
  • these substances include colloidal albumin, agar, gum arabic, dextran, alginic acid; cellulose derivatives such as partially hydrolysed cellulose acetate with 19% to 26% of acetyl content; polyacrylamide, imidized polyacrylamide, casein; urethanecarboxylic group- or cyanoacetyl group-containing vinylalcoholic polymers such as vinylalcoholvinyl cyanoacetate copolymers; polyvinylalcohol-polyvinylpyrrolidone, hydrolysed polyvinyl acetate; polymers obtained from vinyl group-containing monomers, and protein itself or protein saturated with acyl group; polyvinylpyridine, polyvinylamines, polyaminoethyl methacrylate, and polyethyleneimine for example.
  • Silver halide emulsions used in the invention may be allowed to contain various known surface active agents for various purposes such as coating aid, static prevention, slip improvement, dispersion aid, stick prevention; and picture improvement including promotion of development, contrast improvement, and sensitization.
  • Such surface active agents may be allowed to be, for example, nonionic surface active agents including steroid saponins; alkylene oxide derivatives such as polyethene alycol, polyethylene glycol-polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ether polyethylene glycols, polyethylene glycol sorbitan esters, polyalkylene glycol aklylamines or alkylamides, and silicone-polyethylene oxide adducts; glycidol derivatives such as alkenylsuccinic polyglycerides, and alkylphenol polyglycerides; esters of polyhydric alcohols and fatty acids; anion surface active agents, which contain acid groups such as carboxyl, sulfo, phospho, sulfate ester or phosphate ester group, including triterpenoid saponins, alkylcarboxylates, alkylbenzenesulfonates, alkylnaphthalene
  • silver halide emulsions used in the invention may be allowed to contain, besides the above surface active agents, any of imidazole, thioether and selenoether compounds which are described in specification of West German patent application OLS Nos. 2,002,871, 2,445,611 and 2,360,878; and British Pat. No. 1,352,196.
  • ballasted couplers are preferably contained by photosensitive silver halide layers afore-mentioned, then, for example, yellow, magenta and cyan ballasted couplers are used in combination with blue-, green- and red-sensitive silver halide emulsions, respectively.
  • Each of said ballasted couplers preferably has lipophilic group(s) such as 2,4-di-t-amylphenoxyalkaneamido group in its molecule so that it may not diffuse in the photograph-constituting layers.
  • Said coupler is allowed to be used by either 4 or 2 equivalents to silver ion.
  • Colored couplers having color correcting effects or couplers (called DIR couplers) which release development inhibitors during developing treatments are allowed to be contained.
  • Couplers Part of said couplers are allowed to be couplers whose coupling reaction products are colorless.
  • yellow couplers well-known couplers of open-chained ketomethylene type can be used. Among them, compounds of benzoyl acetanilide and pivaloyl acetanilide types are favorably used.
  • Useful yellow couplers are cited in U.S. Pat. Nos. 2,875,057, 3,408,194 and 3,519,429; Japanese Patent O.P.I. Publication Nos. 26133/1972, 29432/1973, 87650/1975, 17438/1976 and 102636/1976; and Japanese Patent Examined Publication Nos. 19956/1970, 33410/1976, 10783/1976 and 19031/1972, for example, and among them, the following compounds are especially favorable: ##STR7##
  • magenta couplers compounds of pyrazolone, indazolone cyanoacetyl pyrazolotriazole and pyrazolinobenzimidazole types can be used, and compounds of pyrazolone type and especially favorable.
  • Useful magenta couplers are cited in U.S. Pat. Nos. 2,600,788, 3,062,053, 3,408,194 and 3,519,429; Japanese Patent O.P.I. Publication Nos. 111631/1974, 29236/1981 and 94752/1982; and Japanese Patent Examined Publication No.
  • cyan couplers compounds of phenol and naphthol types can be used.
  • Useful compounds are cited in U.S. Pat. Nos. 2,423,730, 2,474,293 and 2,895,826; Japanese Patent O.P.I. Publication No. 117422/1975; and Japanese Patent Registration No. 127513, for example, and among them, the following compounds are especially preferable: ##STR9##
  • the above various couplers can be contained also two or more combined together by the same layer.
  • the same compound is allowed to be contained by two or more different layers.
  • the coupler may be dissolved into any of the following solvent system, and then dispersed into the emulsion: dialkyl phthalates such as dibutyl, and dioctyl phthalates; and phosphoric esters such as diphenyl, triphenyl, tricresyl, and dioctyl butyl phosphates; alkylamides such as diethyl lauramide and the like.
  • dialkyl phthalates such as dibutyl, and dioctyl phthalates
  • phosphoric esters such as diphenyl, triphenyl, tricresyl, and dioctyl butyl phosphates
  • alkylamides such as diethyl lauramide and the like.
  • some organic solvents with boiling points ranging from about 30° C.
  • lower alkyl acetates such as ethyl and butyl acetates, ethyl bropionate, sec-butyl alcohol, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate, and methylcellosolve acetate
  • lower alkyl acetates such as ethyl and butyl acetates, ethyl bropionate, sec-butyl alcohol, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate, and methylcellosolve acetate
  • some mixture of the above high and low boiling organic solvents also may be applicable.
  • the obtained solution is dispersed into the hydrophilic colloid system.
  • Certain mixture of the above higher and lower boiling-point organic solvents also are useful.
  • Such a coupler has an acid group such as carboxylic or sulfonic acid group, it is introduced into the hydrophilic colloid system as its alkaline solution.
  • Such a coupler is, in general, added to the colloid system at concentrations ranging from 2 ⁇ 10 -3 moles, to 5 ⁇ 10 -1 moles, preferably from 1 ⁇ 10 -2 mole to 5 ⁇ 10 -1 moles per mole of silver contained in the silver halide emulsion layers.
  • DIR compounds can be used for the photographic material of the invention.
  • Such DIR compounds preferably may be compounds described in U.S. Pat. Nos. 2,327,554, 3,227,554 and 3,615,506; Japanese Patent OPI Application Nos. 82424/1977, 145135/1979 and 151944/1982; and Japanese Patent Examined Publication No. 161141/1976 for example.
  • Especially preferable DIR compounds are as follows: ##STR12##
  • diocetylcellulose As an antistatic agents effectively used in the invention, there are diocetylcellulose; styrene-perfluoroalkyl sodium maleate copolymer; and alkali salt of reaction product from styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid.
  • a matting agent polymethyl methacrylate, polystyrene, and alkali-soluble polymers are useful. Colloidal silica also may be useful.
  • As a latex added for the purpose of improving film properties latices of copolymers of acrylic esters or vinylesters with other ethylene group-having monomers are useful.
  • glycerol or glycol compounds As a plasticizer for gelatin, glycerol or glycol compounds are useful.
  • a thickner styrene-sodium maleate copolymer, alkyl vinyl ether-maleic acid copolymer and the like are useful.
  • a support for the photographic material which is prepared using silver halide emulsion made in such ways as mentioned above there are useful, for example, barite paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, celluldse nitrate, polyvinylacetal, polypropylene; polyester films such as polyethylene terephthalate film; and polystyrene; and the support for the photographic material of the invention is selected among them properly according to the purpose of application.
  • the support is often undercoated at need.
  • the photographic material of the invention prepared using silver halide emulsion can be, after exposure to light, treated for development using common well-known methods. For example, it can be, after color developing, either bleached and fixed simultaneously, and rinsed if necessary, and then stabilized; or bleached and fixed separately, and rinsed if necessary, and then stabilized.
  • color developing agent various aromatic primary amine developing agents such as p-phenylenediamine- and p-aminophenol-type compounds are preferably used.
  • a multilayered color photographic material is prepared by having eight layers which have respective compositions as shown below, form on a support of cellulose triacetate film in order.
  • First layer (a antihalation backing):
  • a layer is formed by coating black colloidal silver-containing gelatin solution by 50 mg silver and 0.5 g gelatine per m 2 .
  • Second layer (the first intermediate layer):
  • a gelatin layer which contains emulsified dispersion of 2,5-di-t-octylhydroquinone.
  • a highly red-sensitive emulsion is prepared by color sensitizing a silver iodobromide emulsion which contains 4 mol % silver iodide and has 0.7 ⁇ average particle size using a mixture of anhydro-5,5'-dichloro-3,3'-di- ⁇ sulfopropyl-9-ethyl-thiacarbocyanine hydroxide pyridium salt and anhydro-9-ethyl-3,3'-di- ⁇ -sulfopropyl-4,5,4',5'-dibenzothiacarbocyanine hydroxide triethylamine salt (4:1).
  • Another gelatin layer which contains emulsified dispersion of 2,5-di-t-octylhydroquinone.
  • Fifth layer (a green-sensitive emulsion layer):
  • a highly green-sensitive emulsion is prepared by color sensitizing a silver iodobromide emulsion which contains 5 mol% silver iodide and has 0.75 ⁇ average particle size using a mixture of anhydro-9-ethyl-5,5'-dichloro-3,3'-di-( ⁇ -sulfopropyl)oxacarbocyanine sodium salt and anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-( ⁇ -sulfopropyl)imidazolocarbocyanine hydroxide triethylamine salt (3:1).
  • the emulsion is stabilized by adding 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
  • An emulsified dispersion which contains 1-(2,4,6-trichlorophenyl)-3-[3- ⁇ -(2,4-di-t-amylphenoxy)acetamido ⁇ -benzamido]-5-pyrazolone, as a ballasted magenta coupler, by 0.08 moles per mole of silver, is added to the former silver halide emulsion.
  • the obtained mixture is referred to the reference control.
  • An aliquot of this control is further added to with an emulsified dispersion which contains the exemplary compound (4) by 0.008 moles per mole of silver.
  • the obtained mixture is referred to the correspondent according to the invention. Both the control and the correspondent are coated by 2, 3 g silver and 2.7 g gelatin per m 2 , respectively.
  • a gelatin layer which contains dispersion of both yellow colloidal silver and 2,5-di-t-octylhydroquinone by 0.1 g silver and 1.2 g zelatin per m 2 .
  • Seventh layer (a blue-sensitive emulsion layer):
  • a highly-sensitive silver iodobromide emulsion in gelatin which contains 6 mol % silver iodide and has 0.8 ⁇ average particle size is added to with a proper amount of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer, and then with an emulsified dispersion which contains d-[4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]- ⁇ -pivalyl-2-chloro-5-[ ⁇ -(2,4-di-t-amylphenoxy)butyramido]acetanilide, as a ballasted yellow coupler, by 0.22 moles per mole of silver.
  • the obtained mixture is referred to the refereence control.
  • a gelatin layer which contains particles of polymethyl methacrylate with 1.5 ⁇ average particle size.
  • Treating soltions available in the above procedures have, for example, the following compositions, respectively:
  • An emulcified dispersion is prepared by adding the exemplary compound (7) to a red-sensitive emulsion similar to the one for the third layer in Example 1 by 0.25 moles per mole of silver. By coating this dispersion by 0.72 g silver and 2.08 g gelatin per m 2 , a layer masking in the red-sensitizing layer is formed between the second and third layers of the sample of the invention (the correspondent) in Example 1.
  • Another emulsified dispersion is prepared by adding the exemplary compound (11) to a green-sensitive emulsion similar to the one for the fifth layer in Example 1 by 0.25 moles per mole of silver.
  • a layer having 2.0 g gelatin per m 2 is formed by coating an emulsified dispersion which contains 0.0017 moles of the exemplary compound (9).
  • a layer having 0.4 g gelatin per m 2 is formed by coating an emulsified dispersion which contains 0.0007 moles of the exemplary compound (8).
  • a layer having 0.6 g gelatin per m 2 is formed by coating an emulsified dispersion which contains 0.00046 moles of the exemplary compound (2).
  • a multilayered color photographic material is prepared by having thirteen layers which have respective compositions as shown below, form on a support of cellulose triacetate film in order.
  • First layer (an antihalation backing):
  • a layer is formed by coating black colloidal silver-containing gelatin solution at 50 mg silver and 0.5 g gelatin per m 2 .
  • Second layer (the first intermediate layer):
  • a gelatin layer which contains emulsified dispersion of 2,5-di-t-octylhydroquinone.
  • a highly red-sensitive emulsion is prepared by color sensitizing a silver indobromide emulsion which contains 4 mol % silver iodide and has 0.7 ⁇ average particle size using a mixture of anhydro-5.5'-dichloro-3,3'-di- ⁇ -sulfopropyl-9-ethyl-thiacarbocyanine hydroxide pyridum salt and anhydro-9-ethyl-3,3'-di- ⁇ sulfopropyl-4,5,4',5'-dibenzothiacarbocyanine hydroxidetriethylamine salt (4:1).
  • the emulsion is stabilized by adding a proper amount of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
  • the exemplary compound (7) by 0.25 moles per mole of silver is dissolved in tricresyl phosphate, and emulsified into another aliquot of gelatin solution, and then is added to the former silver halide emulsion.
  • the third layer is formed by coating the obtained mixture at 0.72 g silver and 2.0 g gelatin per m 2 .
  • Fourth layer (a low red-sensitive emulsion layer):
  • silver iodobromide emulsion for the third layer instead of the silver iodobromide emulsion for the third layer, there is adopted another silver iodebromide emulsion which contains 5 mol % silver iodide and has 0.4 ⁇ average particle size.
  • the exemplary compound (7) for the third layer there are adopted.
  • a gelatin layer which contains emulscfied dispersion of 2,5-di-t-octylhydroquinone.
  • Seventh layer (a layer masking in a green-sensitizing layer):
  • a highly green-sensitive emulsion is prepared by color sensitizing a silver iodobromide emulsion which contains 5 mol % silver iodide and has 0.75 ⁇ average particle size using a mixture of anhydro-9-ethyl-5,5'-dichloro-3,3'-di- ⁇ -sulfopropyl)oxacorbocyanine sodium salt and anhydro-5,6,5',6'-tetracgloro-1,1'-diethyl-3,3'-di-( ⁇ -sulfopropyl)imidazolocarbocyanine hydroxide triethylamine salt (3:1). Then the emulsion is stabilized by adding a proper amount of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
  • An emulsified dispersion which contains the exemplary compound (1) by 0.25 moles per mole of silver is added to the former silver halide emulsion. Then, the seventh layer is formed by coating the obtained mixture at 0.3 g silver and 0.4 g gelatin per m 2 .
  • Eighth layer (a low green-sensitive emulsion layer):
  • silver iodobromide emulsion for the seventh layer there is adopted another silver iodobromide emulsion which contains 4 mol % silver iodide and has 0.35 ⁇ average particle size.
  • the exemplary compound (1) for the seventh layer there is adopted 1-(2,4,6-trichlorophenyl)-3-[3 ⁇ -(2,4-di-t-amylphenoxy)acetamido ⁇ -benzamido]-5-pyrazolone, as a ballasted magenta coupler, by 0.08 moles per mole of silver; 1-(2,4,6-trichlorophenyl)-3-[3- ⁇ -(2,4-di-t-amylphenoxy)acetamido ⁇ benzamido]-4-(4-methoxyphenylazo)-5-pyrazolone, as a colored coupler, by 0.015 moles per mole of silver; and 2-(1-phenyl-5-tetrazolylthio
  • a gelatin layer which contains dispersion of both yellow colloidal silver and 2.5-di-t-octyl-hydroquinone by 0.1 g silver and 1.2 g gelatin per m 2 .
  • a highly sensitive silver iodobromide gelatin solution which contains 6 mole % silver iodide and has 0.8 ⁇ average particle size is stabilized by adding a proper amount of 4-hydroxy-b-methyl-1,3,3a,7-tetrazaindene.
  • An emulsified dispersion which contains the exemplary compound (2) by 0.25 moles per mole of silver is added to the silver halide emulsion.
  • the eleventh layer is formed with 0.2 g silver and 0.6 gelatin per m 2 .
  • Twelfth layer (a blue-sensitive emulsion layer):
  • the twelfth layer is formed with 1.0 g silver and 3.0 g gelatin per m 2 .
  • a gelatine layer which contains particles of polymethyl methacrylate with 1.5 ⁇ average particle size.
  • 2-Hydroxy-4,6-dichloro-s-triazine sodium salt or bis-(vinyl sulfonyl)ethane as a gelatin film stiffner, and a certain surface active agent are added to the gelatine solution for every layer.
  • the photographic material thus obtained exhibits definite color images according to the same exposure and developiing treatments as in Example 1.
  • the third layer (the layer masking in a red-sensitizing layer of Example 4 there is adopted a layer which is formed by coating an emulsified dispersion that contains the exemplary compound (7) by 0.0017 moles, by 0.4 g gelatin per m 2 .
  • the seventh layer (the layer masking in a green-sensitizing layer) of Example 4 there is adopted a layer which is formed by coating an emulsified dispersion that contains the exemplary compound (1) by 0.0007 moles, by 0.4 g gelatin per m 2 .
  • Example 4 instead of the eleventh layer (the layer masking in a blue-sensitizing layer) of Example 4, there is adopted a layer which is formed by coating an emulsified dispersion that contains the exemplary compound (2) by 0.00046 moles, by 0.6 g gelatin per m 2 .
  • the other procedures are carried out according to the same way as in Example 1.
  • the obtained sample exhibits definite color images according to the same exposure and developing treatments as in Example 1.
  • the present invention not only achieves its aimed objects but also makes it possible to provide much sharp color photographic materials with thickness-saving coated layers which lead to cost reductions in production and developing treatment.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US06/774,340 1984-09-14 1985-09-10 Silver halide color photo-sensitive material Expired - Fee Related US4690888A (en)

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JP59195152A JPS6172242A (ja) 1984-09-14 1984-09-14 感光性ハロゲン化銀カラ−写真材料
JP59-195152 1984-09-14

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4833069A (en) * 1986-01-23 1989-05-23 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic light-sensitive material comprising a specified cyan coupler combination and total film thickness
US4871655A (en) * 1987-01-16 1989-10-03 Konica Corporation Light-sensitive silver halide color photographic material containing multi-functional dye
USH782H (en) 1986-09-12 1990-05-01 Silver halide color photographic material
US4968594A (en) * 1986-03-05 1990-11-06 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
US4977072A (en) * 1985-11-27 1990-12-11 Agfa-Gevaert Aktiengesellschaft Color photographic recording material containing color couplers
US4980267A (en) * 1988-08-30 1990-12-25 Eastman Kodak Company Photographic element and process comprising a development inhibitor releasing coupler and a yellow dye-forming coupler
US5019489A (en) * 1989-07-26 1991-05-28 Eastman Kodak Company Color photographic element and process
US5364745A (en) * 1990-12-19 1994-11-15 Eastman Kodak Company Azoaniline masking couplers for photographic materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61184541A (ja) * 1984-08-27 1986-08-18 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
DE3789394D1 (de) * 1986-01-25 1994-04-28 Konishiroku Photo Ind Lichtempfindliches farbphotographisches Silberhalogenidmaterial.
US4840884A (en) * 1987-10-19 1989-06-20 Eastman Kodak Company Photographic element and process comprising a dye releasing group

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US4156608A (en) * 1976-05-06 1979-05-29 Agfa-Gevaert, A.G. Color photographic material with improved color reproduction
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US4567135A (en) * 1983-01-19 1986-01-28 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

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FR2414745A1 (fr) * 1978-01-11 1979-08-10 Kodak Pathe Procede pour former les images en couleurs par diffusion-transfert
GB2082340B (en) * 1980-08-14 1984-05-31 Kodak Ltd Production of photographic masked colour images
GB2089054B (en) * 1980-12-09 1984-05-02 Kodak Ltd Photographic colour process
DE3136293A1 (de) * 1981-09-12 1983-03-24 Agfa-Gevaert Ag, 5090 Leverkusen Fotografisches aufzeichnungsmaterial mit einer vorlaeuferverbindung fuer eine gelbmaske
JPS58147743A (ja) * 1982-02-25 1983-09-02 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料

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US3615225A (en) * 1967-12-21 1971-10-26 Agfa Gevaert Ag Color photographic material
US4029503A (en) * 1973-03-28 1977-06-14 Konishiroku Photo Industry Co., Ltd. Diffusible-dye releasing type dyes which couple to form colorless products
US4026573A (en) * 1976-04-21 1977-05-31 Joseph Skilken & Co. Foldable motor scooter
US4156608A (en) * 1976-05-06 1979-05-29 Agfa-Gevaert, A.G. Color photographic material with improved color reproduction
US4420556A (en) * 1980-09-11 1983-12-13 Eastman Kodak Company Photographic silver halide materials
US4567135A (en) * 1983-01-19 1986-01-28 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4977072A (en) * 1985-11-27 1990-12-11 Agfa-Gevaert Aktiengesellschaft Color photographic recording material containing color couplers
US4833069A (en) * 1986-01-23 1989-05-23 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic light-sensitive material comprising a specified cyan coupler combination and total film thickness
US4968594A (en) * 1986-03-05 1990-11-06 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
USH782H (en) 1986-09-12 1990-05-01 Silver halide color photographic material
US4871655A (en) * 1987-01-16 1989-10-03 Konica Corporation Light-sensitive silver halide color photographic material containing multi-functional dye
US4980267A (en) * 1988-08-30 1990-12-25 Eastman Kodak Company Photographic element and process comprising a development inhibitor releasing coupler and a yellow dye-forming coupler
US5019489A (en) * 1989-07-26 1991-05-28 Eastman Kodak Company Color photographic element and process
US5364745A (en) * 1990-12-19 1994-11-15 Eastman Kodak Company Azoaniline masking couplers for photographic materials

Also Published As

Publication number Publication date
JPS6172242A (ja) 1986-04-14
DE3566310D1 (en) 1988-12-22
EP0174873B1 (en) 1988-11-17
EP0174873A2 (en) 1986-03-19
EP0174873A3 (en) 1986-06-25
JPH0439658B2 (enrdf_load_stackoverflow) 1992-06-30

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